AU765652B2

AU765652B2 - Tyre casing whereof the sidewalls can comprise a glazed film

Info

Publication number: AU765652B2
Application number: AU58275/00A
Authority: AU
Inventors: Francois Bataille; Claude Ringot
Original assignee: Michelin Recherche et Technique SA Switzerland; Michelin Recherche et Technique SA France; Societe de Technologie Michelin SAS
Current assignee: Michelin Recherche et Technique SA France; Societe de Technologie Michelin SAS
Priority date: 1999-07-12
Filing date: 2000-07-12
Publication date: 2003-09-25
Anticipated expiration: 2020-07-12
Also published as: US20010051677A1; DE60003629T2; JP2003504478A; DE60003629D1; WO2001004203A1; AU5827500A; EP1131377A1; EP1131377B1; ES2202148T3; KR20010075058A; JP4796724B2; US6554037B2; KR100648851B1

Description

A tyre, the sidewalls of which may comprise a varnished film: The present invention relates to a tyre comprising sidewalls which comprise a vulcanised composition based on at least one elastomer, and a process for forming an even, varnished film on at least one of said sidewalls. The invention applies in particular to the protection of said tyre against the effects of the migration of antioxidants and antiozonants present in said sidewalls, which effects are visible on the respective outer faces of said sidewalls.

It is known that certain rubber compositions are very susceptible to the action of ozone. This is the case in particular with vulcanised compositions based on diene elastomers.

When an article comprising such a vulcanised elastomeric composition is subjected to prolonged static and dynamic stresses in the presence of ozone, more or less marked cracks or fissures appear which are visible on the surface of the article. These cracks are oriented substantially perpendicular to the direction of said stress, and the propagation thereof under the action of such a persisting stress may eventually cause complete breaking of the article.

In order to minimise these effects of ozone, provision has been made to integrate in these articles and, in particular, in the sidewalls based on elastomers which form part of the tyres, antiozonants which are intended to reduce the formation and propagation of cracks under the aforementioned conditions, and also waxes, which are intended to form a protective coating on the surface of the sidewalls so as to ensure additional protection under static stresses.

The association of these antiozonants and these waxes has proved the effectiveness thereof in minimising cracks on the surface of the sidewalls.

Unfortunately, the most effective antiozonants are also characterised by a very great aptitude to migrate across the elastomer substrate and to stain and colour the surfaces adjacent to said substrate. More precisely, yellowish or brown marks are observed on the surfaces of said sidewalls. This phenomenon is known by the name "coloration".

Furthermore, it turns out that the waxes also migrate to the surface of the sidewalls, the effect of this migration being to make said surface dull and grey, or even whitish. This phenomenon is known by the name "efflorescence".

2 The object of the present invention is to propose a tyre including sidewalls which include a vulcanised composition based on at least one elastomer, which makes it possible to overcome the disadvantages caused by these undesirable phenomena.

With the aforementioned object in mind in one aspect the present invention provides a tyre having sidewalls which include a vulcanised composition based on at least one elastomer, said composition including, in combination: in a quantity of between 0.3 and 5 phr, a polymer including, on either side of an oxy radical of the formula respectively an alkyl group and at least one alkene polyoxide block of the formula (CnH 2 nO)z which is joined to a hydrogen atom at the chain end, such that said hydrogen atom forms an alcohol function with the end atom of oxygen of said alkene polyoxide, and in a quantity of between 0.5 and 10 phr, an alkali metal salt of an alkylsulphonic or alkylsulphuric acid.

The incorporation of this polymer and this alkali salt in said elastomer or elastomers in order to form said vulcanised elastomeric composition permits later formation of an even, varnished film on the respective outer faces of the sidewalls of the vulcanised tyre, following a greater or lesser time spent in an atmosphere, the ozone content of which is substantially at least 4 parts per hundred million, 20 such as a moderately polluted urban atmosphere.

i: This even film has the advantage of giving said sidewalls a non-stained appearance, such that the aforementioned undesirable effects of said S'0 phenomena of coloration and efflorescence are thus completely overcome.

oo Furthermore, said film imparts a varnished appearance to said sidewalls, that is to say, one which shines like varnish, which significantly improves their aesthetic appearance.

According to one embodiment of the invention, said polymer having an oxy i0"0: radical includes polyoxyethylene and polyoxypropylene blocks.

0* In this case, said polymer having an oxy radical corresponds for example 30 to the formula: 0. R-O-(C 3

H

6 0)x-(C 2

H

4 0)y-H, in which R is a blend of alkyl groups having from 13 to 15 carbon atoms (R has a majority of 14 carbon atoms), the molecular weight of said polymer having an oxy radical being from 500 g/mol to 1100 g/mol, x possibly varying substantially from 3 to 15 and y possibly varying substantially from 3 to This polymer having an oxy radical advantageously has a molecular weight which is substantially equal to 670 g/mol (in this case, x is equal or substantially equal to 5 and y is equal or substantially equal to or to 510 g/mol (in this case, x and y are each equal or substantially equal to or alternatively to 1050 g/mol (in this latter case, x is equal or substantially equal to 15 and y is equal or substantially equal to 4).

Preferably, said polymer having an oxy radical is present in said composition in a quantity substantially equal to 2 phr.

According to one embodiment of the invention, said alkali metal salt is a sodium salt present in said composition in a quantity substantially equal to 5 phr, and corresponding to the formula: R'-SOz-Na, in which R' is a blend of alkyl groups having from 3 to 17 carbon atoms, and z is an integer equal to 3 or 4.

In the case in which said salt is of the formula R'-S0 3 -Na, R' may for example have a majority of 8 carbon atoms or alternatively 15 carbon atoms.

In the case in which said salt is of the formula R'-S0 4 -Na, R' may for example have a majority of 8 carbon atoms or alternatively 13 carbon atoms.

According to another characteristic of the invention, said elastomeric 20 composition includes at least one antiozonant and/or at least one antioxidant.

Said antiozonant belongs, for example, to the group consisting of 2,4,6tris(N-1,4-dimethyl-pentyl-p-phenylene-diamino)-1,3,5-triazine and N,N'-di(1,4dimethylpentyl)-p-phenylenediamine.

.:As for said antioxidant, it is constituted, for example, of N-(1,3dimethylbutyl)-N'-phenyl-p-phenylenediamine.

A further aspect of the present invention provides a process for forming an even, varnished film on the outer face of at least one of the sidewalls of a tyre including using a tyre according to the present invention, and exposing, statically S. for at least 48 hours, in a chamber kept at a temperature substantially equal to or S' 30 greater than 25°C, said or each sidewall to an ozone environment which is such that the concentration of ozone metered into the ambient air is substantially equal to or greater than 20 parts per 100 million, for forming said film with an obtained Sthickness of the latter substantially equal to or greater than 0.5 microns.

Preferably, said concentration of ozone metered into the ambient air is substantially equal to or greater than 40 parts per 100 million.

This film also has the advantage of providing said sidewalls with a non-stained appearance, such that the aforementioned undesirable effects are overcome in the same manner, with a glossy appearance of said or each sidewall being obtained.

The aforementioned characteristics of the present invention, as well as others, will be better understood on reading the following description of several examples of embodiment of the invention, which are given by way of illustration and not of limitation.

In the following examples, the molecular weights were measured by the tonometry technique, by means of a vapour pressure osmometer sold under the name "WESCAN model 232A". For these measurements, "RP" toluene was used as solvent, and a measurement temperature of 50'C was used.

CONTROL EXAMPLE The following mixture formulation, in parts by weight per hundred parts of elastomer (phr), was used for a vulcanised rubber composition intended to form the sidewalls of a "control" tyre: natural rubber: 35 phr polybutadiene: 65 phr carbon black N660: 60 phr aromatic oil: 20 phr "6PPD": 3 phr "Durazone 37": 0.5 phr sulphur: 1.5 phr "CBS": 1 phr zinc oxide: 3 phr stearic acid: 1 phr, where "6PPD" is N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, which is both an antioxidant and an antiozonant, "Durazone 37" is the trade name of an antiozonant formed of a paraphenylenediamine-tri-substituted triazine, the name of which is 2,4,6-tris(N-1,4dimethylpentyl-p-phenylene-diamino)-1,3,5-triazine, and "CBS" is N-cyclohexyl-benzothiazyl-sulphenamide, a vulcanisation accelerator.

At the end of a certain time, on the outer face of each sidewall of this control tyre, yellow and brown stains and a generally matte appearance were noted, owing to the migration of the antioxidants and antiozonants.

EXAMPLES 1 to 16 ACCORDING TO THE INVENTION EXAMPLE 1: There was added to the rubber composition corresponding to the formulation of said control example, for the mixing operation in the non-vulcanised state: an antistatic agent A sold by the company CLARIANT under the name HOSTASTAT HS1, in an amount of 5 phr.

This is a sodium salt of an alkylsulphonic acid corresponding to the formula R-S0 3 -Na, in which R is a blend of alkyl groups having 3 to 17 carbon atoms respectively, and having a majority of 15 carbon atoms; and a surfactant B sold by ICI under the name SYNPERONIC LF/RA 280, in an amount of 2 phr.

This is a polymer comprising, on either side of an oxy radical of formula respectively a blend R of alkyl groups having from 13 to 15 carbon atoms, and polyoxyethylene and polyoxypropylene blocks, in accordance with the formula:

R-O-(C

3

H

6 0) 5

-(C

2

H

4 0) 4

-H,

More precisely, the polyoxyethylene block is linked to a hydrogen atom at the chain end, such that the latter forms an alcohol function with the end oxygen atom of said polyoxyethylene block.

The molecular weight of this surfactant B, measured by the aforementioned tonometry technique, is substantially 670 g/mol.

EXAMPLES 2 to 7: In each of the examples 2 to 7, the 0.5 phr of "Durazone 37" (used in said control example) has been replaced by 1 phr of another antiozonant sold under the name "Santoflex 77", which is N,N'-di-(1,4-dimethylpentyl)-p-phenylenediamine. This new base formulation serves as a reference for Examples 2 to 7 below.

Example 2: There was added to this base formulation, for the mixing operation in the nonvulcanised state: the antistatic agent A "HOSTASTAT HS1" of Example 1, in the same amount of phr, the surfactant B "SYNPERONIC LF/RA 280" of Example 1, in the same amount of 2 phr.

Example 3: There was added to said base formulation, for the mixing operation in the nonvulcanised state: the antistatic agent A "HOSTASTAT HS1" of Example 1, in the same amount of phr, a surfactant B sold by ICI under the name SYNPERONIC LF/RA 260, in an amount of 2 phr. This is a polymer comprising, on either side of an oxy radical of formula respectively a blend R of alkyl groups having from 13 to 15 carbon atoms, and polyoxyethylene and polyoxypropylene blocks, in accordance with the formula:

R-O-(C

3

H

6 0)x-(C 2

H

4 0)y-H, with x and y each being equal or substantially equal to 3.

The molecular weight of this new surfactant B, measured by the aforementioned tonometry technique, is substantially 510 g/mol.

Example 4: There was added to said base formulation, for the mixing operation in the nonvulcanised state: the antistatic agent A "HOSTASTAT HS1" of Example 1, in the same amount of phr, a surfactant B sold by ICI under the name SYNPERONIC LF/RA 310, in an amount of 2 phr. This is a polymer comprising, on either side of an oxy radical of formula respectively a blend R of alkyl groups having from 13 to 15 carbon atoms, and polyoxyethylene and polyoxypropylene blocks, in accordance with the formula:

R-O-(C

3

H

6 0)x-(C 2

H

4 0)y-H, with x being equal or substantially equal to 15 and y being equal or substantially equal to 4.

The molecular weight of this new surfactant B, measured by the aforementioned tonometry technique, is substantially 1050 g/mol.

Example There was added to said base formulation, for the mixing in the non-vulcanised state: an antistatic agent A formed of a sodium octanesulphonate sold by STEPAN under the name "BIO-TERGE PAS-8 S" which had been dried beforehand, in an amount of 5 phr, the surfactant B "SYNPERONIC LF/RA 280" of Example 1, in the same amount of 2 phr.

Example 6: There was added to said base formulation, for the mixing in the non-vulcanised state: an antistatic agent A formed of a sodium octylsulphonate sold by RHODIA under the name "RHODAPON OLS" which was dried beforehand, in an amount of 5 phr, the surfactant B "SYNPERONIC LF/RA 280" of Example 1, in the same amount of 2 phr.

Example 7: There was added to said base formulation, for the mixing operation in the nonvulcanised state: an antistatic agent A formed of a sodium tridecylsulphate sold by RHODIA under the name "RHODAPON TDS" which was dried beforehand, in an amount of 5 phr, the surfactant B "SYNPERONIC LF/RA 280" of Example 1, in the same amount of 2 phr.

EXAMPLES 8 to 16: For all these examples 8 to 16, there was added to the rubber composition corresponding to the formulation of said control example, with the exception of the amounts of "6PPD" and "Durazone 37" used (different amounts specified below), for the mixing in the non-vulcanised state: said antistatic agent A sold under the name "HOSTASTAT HS1", in amounts of between 0.5 and 10 phr, and said surfactant B sold under the name "SYNPERONIC LF/RA 280", in an amount of between 0.3 and 5 phr, The table below sets forth the amounts of antistatic agents A, surfactant B, "6PPD" and "Durazone 37" used for each of these Examples 8 to 16.

ex. 8 ex. 9 ex. 10 ex. 11 ex. 12 ex. 13 ex. 14 ex. 15 ex. 16 agent A 1 3 7 9 5 5 5 5 Agent B 2 2 2 2 0.5 1 3 4 2 "6PPD" 3 3 3 3 3 3 3 3 0 "Durazone 37" 1 1 1 1 1 1 1 1 1 PLACEMENT IN AN ATMOSPHERE MORE OR LESS RICH IN OZONE OF RUBBER COMPOSITIONS VULCANISED IN ACCORDANCE WITH ONE OR OTHER OF EXAMPLES 1 TO 16 ACCORDING TO THE INVENTION: 1) In a first mode of placement, the vulcanised tyres obtained respectively in accordance with Examples 1 to 16 were placed in static conditions in an outdoor atmosphere of urban type, at 200C and sheltered from the sun and rain. This atmosphere is such that the concentration of ozone metered into the atmospheric air is substantially 4 parts per 100 million. This placement was effected so as to expose each sidewall to this open atmosphere, for a period of 2 months.

Surprisingly, at the end of this placement, the presence of an even, varnished film, that is to say, one which shines or gleams like varnish, was noted on the outer face of each sidewall. More precisely, this film had an average thickness of about 0.8 pm. No stain, soiling or dull area was visible on the sidewalls, unlike the control example.

2) In a second mode of placement, the tyres vulcanised in accordance with Examples 1 to 16 were placed in static conditions in an outdoor atmosphere of urban type, at 250C and sheltered from the sun and rain. This atmosphere is also such that the concentration of ozone metered into the atmospheric air is close to 4 parts per 100 million.

This placement was effected so as to expose each sidewall to this open atmosphere, this time for a period of 5 months.

As in said first mode, at the end of this placement, the presence of a varnished film of an average thickness also close to 0.8 pm was noted, such that the sidewalls were completely devoid of stains and had a glossy appearance.

3) In a third mode of placement, the tyres vulcanised in accordance with Examples 1 to 16 were placed in static conditions in an ozonation enclosure, formed of a closed chamber, the concentration of ozone metered into the air of which was about 40 parts per 100 million, and the internal temperature of which was 25 0 C. This placement was effected so as to expose each sidewall to this closed atmosphere, for a period of 7 days.

As in said first mode, at the end of this placement, the presence of an even, varnished film of an average thickness also close to 1 pm was noted, such that the sidewalls were completely devoid of stains and had a glossy appearance.

4) In a fourth mode of placement, the tyres vulcanised in accordance with Examples 1 to 16 were placed in static conditions in an ozonation enclosure, formed of a closed chamber, the concentration of ozone metered into the air of which was this time about parts per 100 million, and the internal temperature of which was 38°C. This placement was effected so as to expose each sidewall to this closed atmosphere, for a period of 24 or 72 hours.

As previously, at the end of this placement, the presence of an even, varnished film of an average thickness also close to 1 pm was noted, such that the sidewalls were completely devoid of stains and had a glossy appearance.

5) In a fifth mode of placement, the tyres vulcanised in accordance with Examples 1 to 16 were placed in static conditions in an ozonation enclosure, formed of a closed chamber, the concentration of ozone metered into the air of which was about 200 parts per 100 million, and the internal temperature of which was 25 0 C. This placement was effected so as to expose each sidewall to this closed atmosphere, for a period of 48 hours.

As previously, at the end of this placement, the presence of an even, varnished film of an average thickness of 1.5 pm was noted, such that the sidewalls were completely devoid of stains and had a glossy appearance.

6) In a variant of each of these modes of placement, the tyres which had undergone the ozonation treatment in an enclosure in accordance with each of the last three aforementioned modes were placed in the open air and in static conditions, under the conditions specified for said first and second modes.

The same results were obtained of sidewalls covered with a varnished film, with an average thickness close to 1.5 pm.

For each of the tyres having being placed in accordance with one or another of the above 6 modes, the following qualitative tests were performed to evaluate the performance.

"coloration/efflorescence": test of the ability of the varnished films thus formed to withstand the effects of the aforementioned coloration and efflorescence phenomena, which are due to the surface migration of the antiozonants; "dynamic strength": test of the mechanical strength of said films under dynamic stress, consisting in covering 12,000 kilometres on a roller with an imposed deflection of at 60 kilometres per hour, this test imposing a dynamic deformation at the surface of the sidewalls of the order of 15% extension; "kerb scraping": rubbing of the sidewalls provided with said films against a kerb for several metres to determine any detachment or disappearance of said films; "water": test of the resistance of said films when immersed in water for 4 hours; this simulates long-duration parking of a vehicle in a puddle of water in a parking lot, for example; "washing": test of the resistance of said films to washing by rubbing with an aqueous solution comprising soap.

The results obtained are set forth in the table below.

coloration/efflorescence none; even, varnished appearance dynamic strength even, varnished film maintained kerb scraping film disappeared water gradual degradation of the film washing film disappeared It will be noted that the films immersed in water disappear only very gradually over time.

Furthermore, "test pieces" comprising respectively the compositions vulcanised in accordance with Examples 1 to 16 according to the invention were subjected to ozonisation, following the above fourth mode of placement (in a chamber containing 50 parts per 100 million of ozone, at 38°C, for 24 hours and with static surface deformation under extension of 18%).

The degree of gloss of these "test pieces" 1 to 16 was measured, so as to provide objective characterisation of the varnished nature of the films thus obtained.

To this end, plates of rubber vulcanised by means of a so-called "Teflon-coated" mould then treated with ozone as indicated above were used for these "test pieces", each one being formed of a stack of two half-plates. Each half-plate has a height of 1.5 mm, a length of 15 cm and a width of 14 cm.

Each upper plate is formed of a sidewall mix in accordance with one or other of Examples 1 to 16. As for each lower plate, it is formed of a sidewall mix in accordance with said control example.

This vulcanisation in a "Teflon-coated" mould was effected in order to obtain for each half-plate a given surface state which therefore characterises both the control composition and the composition according to the invention and which, consequently, determines said desired gloss measurements.

This "Teflon-coated" mould is defined, firstly, by the steel forming it, which is of the Z3 CN 18-10 type (AFNOR nomenclature) and, secondly, by the treatment using jets of projectiles followed by "Teflon-coating" to which it is subjected.

This treatment using jets of projectiles is intended to obtain a given roughness value Ra (arithmetic mean deviation of the profile) which is between 2 and 4 pm.

For all the roughness measurements, a surface-roughness tester sold under the name "MITUTOYO, SURTRONIC series" is used.

More precisely, the length Lm of evaluation of the roughness on the plates is selected to be 4 mm, and the elementary length (threshold Le of measurement by the sensor of the surface-roughness tester, or cut-off) is selected to be 0.8 mm. Furthermore, the filter used for this elementary length is of the "pc50" type, with a size f 5 pm.

Said sensor is a diamond-type sensor, and its speed of displacement is 0.25 mm/s.

This treatment with jets of projectiles is effected at a pressure of 3 bar, at a jet distance of 10 cm and with a normal incidence. The projectiles used are formed of particles of white corundum (alumina), which have an average size of 80 pm and a standardised size of 150 mesh (in accordance with Standard NF XII-508).

The later "Teflon-coating" treatment consists: in a first stage, of spraying polytetrafluoroethylene on to the inner face of the mould wall, so as to obtain a thickness of sprayed material of 10 to 15 pm on said face. Then it is dried at 2500C for 5 minutes, then cooled, and in a second stage, of again spraying polytetrafluoroethylene on to said inner face, to obtain a thickness of sprayed material of 5 to 10 pm on said face. It is then dried at 1100C for 5 minutes, followed by curing at 3900C for 45 minutes, followed by cooling.

Finally, a roughness value Ra of between 0.5 and 1.2 pm is obtained for the inner face of the mould wall, this range thus determining a given surface state for the two halfplates which have been vulcanised and treated with ozone, for the gloss measurements.

The latter are performed using a reflectometer sold under the name "TRI-gloss BYK Gardner". This apparatus conforms to standard ASTM D523 or ISO 2813.

For all the "test pieces" 1 to 16, the presence of an even, varnished film rendering them completely devoid of stains and imparting thereto a glossy appearance was noted.

The following table shows, for three different angles of incidence, results of the degree of gloss obtained for the compositions which were vulcanised and treated with ozone in accordance with Examples 1 to 16 of the invention, compared with a control variant of vulcanised composition which differs from that of said control example only in that it does not comprise any "Durazone 37" (the vulcanised composition was subjected to ozonisation in an enclosure under conditions identical to those of Examples 1 to 16, that is to say, following the above fourth mode of placement).

T ex. ex. ex. ex. ex. ex. ex. ex. ex. ex. ex. ex. ex. ex. ex. ex.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 degree of gloss, 0.5 7.2 3.7 2.2 1.4 5.2 10.0 11.0 6.3 6.6 3.8 3.4 4.9 4.5 4.6 6.9 3.4 incidence 200 degree of gloss, 6.5 38.7 24.2 16.9 11.6 32.0 47.0 45.0 35.7 37.5 27.0 25.8 32.9 30.3 31.8 37.1 24.1 incidence degree of gloss, 22.4 39.4 24.7 20.0 13.0 26.0 43.0 25.0 34.6 36.7 27.7 28.3 37.3 33.5 34.3 38.9 25.0 incidence 850 This table shows that the film formed by means of compositions according to the invention which have been subjected to the afore-mentioned ozonisation is of varnished nature, that is to say that it is characterised by high specular reflection which imparts thereto this degree of gloss of greater or lesser intensity, unlike the control composition which is characterised by diffuse reflection which imparts conventional matteness thereto.

By way of comparison of the varnished appearance of the film obtained according to the invention with films known for making sidewalls shine, which films do not form on the surface of the latter as in the invention, but are formed of a varnish, that is to say, a solution which is applied to said sidewalls, reference may be made to the varnish sold under the name "LYNDCOAT BR 790" by Rh6ne-Poulenc. This varnish in fact has a degree of gloss of the same order of magnitude as the varnished film according to the invention, under analogous measurement conditions starting from a surface state close to that selected for the gloss measurements referred to above.

It will be noted that the varnished films with which the tyres according to the invention are provided are such that they clearly show the different markings usually applied to sidewalls, during the building thereof and during later testing. Advantageously, it is even noted that, owing to the presence of this film, the sidewall markings are visible with a contrast which is superior compared with the rest of the outer face of said sidewalls.

It will also be noted that the varnished films of the tyres according to the invention remain practically intact after being used in travel.

Claims

1. A tyre having sidewalls which include a vulcanised composition based on at least one elastomer, said composition including, in combination: in a quantity of between 0.3 and 5 phr, a polymer including, on either side of an oxy radical of the formula respectively an alkyl group and at least one alkene polyoxide block of the formula (CnH 2 nO)z which is joined to a hydrogen atom at the chain end, such that said hydrogen atom forms an alcohol function with the end atom of oxygen of said alkene polyoxide, and in a quantity of between 0.5 and 10 phr, an alkali metal salt of an alkylsulphonic or alkylsulphuric acid.

2. A tyre according to Claim 1, wherein said polymer having an oxy radical includes polyoxyethylene and polyoxypropylene blocks.

3. A tyre according to Claim 2, wherein said polymer having an oxy radical corresponds to the formula: R-O-(C 3 H 6 0)x-(C 2 H 4 0)y-H, in which R is a blend of alkyl groups having from 13 to 15 carbon atoms, the molecular weight of said polymer having an oxy radical being from 500 g/mol to 1100 g/mol.

4. A tyre according to Claim 3, wherein said polymer having an oxy radical is such that x varies substantially from 3 to 15 and y varies substantially from 3 to A tyre according to Claim 3 or 4, wherein said polymer having an oxy radical has a molecular weight which is substantially equal to 670 g/mol.

6. A tyre according to Claim 5, wherein said polymer having an oxy radical is such that x is equal or substantially equal to 5 and y is equal or substantially 25 equal to 4.

7. A tyre according to Claim 3 or 4, wherein said polymer having an oxy radical has a molecular weight which is substantially equal to 510 g/mol. 17

8. A tyre according to Claim 7, wherein said polymer having an oxy radical is such that x is equal or substantially equal to 3 and y is equal or substantially equal to 3.

9. A tyre according to Claim 3 or 4, wherein said polymer having an oxy radical has a molecular weight which is substantially equal to 1050 g/mol. A tyre according to Claim 9, wherein said polymer having an oxy radical is such that x is equal or substantially equal to 15 and y is equal or substantially equal to 4.

11. A tyre according to any one of the preceding claims, wherein said polymer having an oxy radical is present in said composition in a quantity substantially equal to 2 phr.

12. A tyre according to any one of the preceding claims, wherein said alkali metal salt is a sodium salt corresponding to the formula: R'-SOz-Na, in which R' is a blend of alkyl groups having from 3 to 17 carbon atoms, and z is an integer equal to 3 or4.

13. A tyre according to Claim 12, wherein said salt corresponds to the formula R'-S0 3 -Na.

14. A tyre according to Claim 13, wherein R has a majority of 8 carbon atoms.

15. A tyre according to Claim 13, wherein R' has a majority of 15 carbon atoms.

16. A tyre according to Claim 12, wherein said salt corresponds to the formula R'-S0 4 -Na.

17. A tyre according to Claim 16, wherein R' has a majority of 8 carbon atoms. 18

18. A tyre according to Claim 16, wherein R' has a majority of 13 carbon atoms.

19. A tyre according to any one of the preceding claims, wherein said salt is present in said composition in a quantity substantially equal to 5 phr.

20. A tyre according to any one of the preceding claims, wherein said elastomeric composition includes at least one antiozonant and/or at least one antioxidant.

21. A tyre according to Claim 20, wherein said antiozonant belongs to the group consisting of 2,4,6-tris(N-1,4-dimethylpentyl-p-phenylenediamino)-1,3,5- triazine and N,N'-di(1,4-dimethylpentyl)-p-phenylenediamine.

22. A tyre according to Claim 20 or 21, wherein said antioxidant is N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine.

23. A process for forming an even varnished film on the outer face of at least one of the sidewalls of a tyre, said process including using a tyre according to any 15 one of the preceding claims, and exposing, statically for at least 48 hours, in an enclosure kept at a temperature substantially equal to or greater than 25°C, the or S each sidewall of said tyre to an ozone environment which is such that the concentration of ozone metered into the ambient air is substantially equal to or greater than 20 parts per 100 million, for forming said film with an obtained thickness of the latter substantially equal to or greater than 0.5 microns.

24. A process according to Claim 23, further including using a concentration of *.ozone metered into the ambient air which is substantially equal to or greater than 40 parts per 100 million.

25. A tyre substantially as hereinbefore described with reference to any one of 25 Examples 1 to 16. 19

26. A process substantially as hereinbefore described with reference to any one of Examples 1 to 16. DATED this 3 1 st day of July 2003 MICHELIN RECHERCHE ET TECHNIQUE SA and SOCIETE DE TECHNOLOGIE MICHELIN WATERMARK PATENT TRADE MARK ATTORNEYS PO BOX HAWTHORN VIC 3122 AUSTRALIA P19072AU00 *g e* *e ••go* *ooo